Optical device

ABSTRACT

An optical device comprising a stack of the following layers: a capping layer (16) having a high refractive index for guiding incident light; a layer of light absorber material (10), preferably a phase-changing material; and a reflective layer (12), wherein the refractive index of the capping layer is at least 1.6.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage application under 35 U.S.C. 371 ofPCT Application No. PCT/GB2016/053196, having an international filingdate of 14 Oct. 2016, which designated the United States, which PCTapplication claimed the benefit of Great Britain Patent Application No.1518371.8 filed 16 Oct. 2015, the contents of each of which areincorporated herein by reference in their entirety.

The present invention relates to an optical device.

There has been a desire for improved optical devices whose spectralcharacteristics can be customised, for example for color filters forspectrometry, or for color displays if the device is switchable.

A prior proposal for a device works on the principle of interferenceusing reflection at the opposite surfaces of an optically transmissivelayer (i.e. like an etalon); this provide a spectral response (i.e.color) in reflection or transmission. The spectrum (color) can be set byincorporating a layer of light absorber material. If the light absorbermaterial is a phase change material (PCM), then the optical propertiesof the device can be switched by switching the phase of the PCM.

However, observable color contrast can only be created if ultra-thin PCMlayers are used, such as 7 nm. This is problematic if devices arefabricated on rough substrates, such as flexible polymers.

Another idea is to use a liquid crystal material as the switchableelement of a display. However, conventional devices need a minimumthickness of 1-2 microns of liquid crystal (depending on thebirefringence of the liquid crystal used). This thickness limits themaximum switching speed, as well as using more material, and making thedevice thicker. Other concepts employ electro-optically activematerials, but these usually require very high voltages, such as 10 kV,which are problematic to generate.

The present invention has been devised in view of the above problems.

Accordingly, the present invention provides an optical device comprisinga stack of the following layers: a capping layer; a layer of lightabsorber material; and a reflective layer, wherein the refractive indexof the capping layer is at least 1.6.

Another aspect of the invention provides an optical device comprising astack of the following layers: a capping layer; a layer of lightabsorber material; a layer of optically active material; and areflective layer.

Further optional aspects are defined in the dependent claims.

Throughout this specification, the terms ‘optical’ and ‘light’ are used,because they are the usual terms in the art relating to electromagneticradiation, but it is understood that in the context of the presentspecification they are not limited to visible light. It is envisagedthat the invention can also be used with wavelengths outside the visiblespectrum, such as infrared and ultraviolet light.

Embodiments of the invention will now be described, by way of exampleonly, with reference to the accompanying drawings in which:

FIG. 1 is a schematic cross-section of a portion of an optical deviceaccording to an embodiment of the invention for devices;

FIG. 2 shows plots of reflectivity against wavelength for devicesaccording to an embodiment of the invention;

FIGS. 3(a) and 3(b) are chromaticity diagrams showing the color gamutachievable with (a) conventional devices, and (b) devices according toembodiments of the invention;

FIG. 4 is a schematic illustration in cross-section of anotherembodiment of the invention comprising a liquid crystal layer;

FIG. 5 is a schematic illustration in cross-section of a furtherembodiment of the invention comprising a liquid crystal layer;

FIG. 6 shows plots of reflectivity against wavelength for devicesaccording to an embodiment of the invention based on the structure ofFIG. 4;

FIG. 7 is a schematic illustration in cross-section of an embodiment ofthe invention comprising an electro-optically active material layer;

FIG. 8 is a schematic illustration in cross-section of a furtherembodiment of the invention comprising an electro-optically activematerial layer;

FIG. 9 shows plots of reflectivity against wavelength for a device withdifferent applied voltages according to an embodiment of the inventionbased on the structure of FIG. 7;

FIG. 10 shows plots of reflectivity against wavelength for devicesaccording to an embodiment of the invention based on the structure ofFIG. 7, with different applied voltages and different thickness ofelectro-optically active material layer; and

FIG. 11 shows an example stack comprising a capping layer formed from aplurality of capping layer sub-layers and a spacer layer formed from aplurality of spacer layer sub-layers;

FIG. 12 shows an example stack comprising a layer of passive lightabsorber material provided within a capping layer;

FIG. 13 shows an example stack comprising a layer of passive lightabsorber material provided within a spacer layer;

FIG. 14 shows an example stack comprising a layer of passive lightabsorber material provided within a capping layer and a layer of passivelight absorber material provided within a spacer layer;

FIG. 15 shows an example stack formed on an optically thick cover sheet;and

FIG. 16 shows a device having a plurality of regions providing differentspectral responses.

A first embodiment of an optical device will now be described withreference to FIG. 1, which shows schematically a layered structure incross-section. A solid layer of light absorber material 10 is provided.This layer is also knows as a thin film absorber, and the materialtypically has an imaginary component of refractive index (k) that isnon-zero over a wide range of wavelengths. Many suitable materials canbe used, and some specific examples are given later. The layer 10 isgenerally more than 10 nanometres thick. In this specific embodiment,the absorber material is Ge₂Sb₂Te₅ (GST).

The absorber material layer 10 is provided on a reflective layer 12(partially or totally reflective, depending on whether the device isbeing used in a transmissive mode or not).

In an earlier proposal, a spacer layer would be sandwiched between theabsorber layer 10 and the reflective layer 12, and a capping layer ofsilica or ITO (indium tin oxide) would be provided on the front (top)side of the device. Conventionally, the capping layer didn't contributeto the color performance, and the absorber layer had to be ultra-thin.

In contrast, in this specific embodiment, a material with highrefractive index (in this case real component of refractive index; theimaginary component of refractive index should be as small as possibleso the material is as transparent as possible) is used as a cappinglayer 16. The refractive index is greater than 1.6, such as 1.8 or more,and can be more than 2.0 or even 2.2. Examples of materials for thecapping layer 16 include TiO₂, ZnO, AgO, diamond, SiO₂, SiN, and TaO.Light entering the high-refractive index capping layer 16 tends toremain in the layer more than in a conventional device (in the same waythat light can be confined in a waveguide, such as an optical fiber).Color is generated through interference with the ‘leaky’ absorber layerand lower interface. The requirement for an ultra-thin absorber layer isremoved. In the case of GST as a PCM comprising the absorber layer 10,when the GST is in the amorphous phase it is less absorbent and thelight in the capping layer 16 is less affected; when the GST is in thecrystalline phase it is more absorbent (more metallic), and so lightleaks at specific wavelengths generating color and color modulation byinterference.

A spacer layer (not shown) can still optionally be provided between thelayers 10 and 12. If the absorber layer 10 is a PCM, then electrodes canbe provided, if required, to switch the phase of the layer (electricallyor thermally), i.e. by applying a suitable voltage pulse from a voltagesource, the PCM can undergo an induced reversible phase. The reflectivelayer 12 can act as a bottom electrode (or so could an optional spacerlayer, if conductive, such as ITO); and a second electrode (not shown)in contact with the PCM can be provided at the side or on top (betweenthe layers 10 and 16). Alternatively, as described in WO 2015/097468 A1or EP16000280.4 for example, the PCM layer may be activated by heatpulses supplied by a heating element adjacent to the PCM, or on anopposite side of the mirror layer to the PCM. In this case, the spacerlayer may be non-conductive and selected solely for its optical andthermal properties.

FIG. 2 shows examples of spectral responses for devices in which thecapping layer 16 of TiO₂ is 10, 50 and 100 nanometres thick; the dashedlines being when the GST is in the amorphous phase and the solid linesbeing when the GST is in the crystalline phase. As can be seen in theseexamples, the color can shift from pale to bright during switching.Using this structure one can create RGB-type pixels in which on state ispale (almost white) and the other state is a bright primary color (suchas bright blue, red or green). Using a thinner capping layer 16, thedevice can have quite a flat spectrum, or so simply be used to switchbetween bright and dark states of pixels. In all of the examples of FIG.2, the reflective layer 12 is a 100 nm thick layer of Ag.

The thickness of the absorber layer 10 can itself generate colorindependently.

The structure of FIG. 1 can easily be integrated with architecturesknown from PCM memory devices on top of CMOS circuitry by changing thetop electrode to the high refractive index layer 16 on top of a thintransparent electrode layer (such as 10 nm ITO).

Using devices according to embodiments of the present aspect of theinvention, the gamut (range of colors accessible in color space) can beimproved dramatically. The points plotted in the chromaticity diagram ofFIG. 3(a) show the previously possible gamut using an ITO capping layer,whereas FIG. 3(b) shows the much larger gamut possible with ahigh-refractive index capping layer 16, in this example the cappinglayers is diamond (e.g. synthetic diamond grown by CVD).

In further embodiments of the invention, either or both of the spacerlayer and capping layer may comprise “composite” layers, which comprisemultiple layers of material having different refractive indices. In thisway, further partial internal reflections are generated at theinterfaces of these multiple layers, providing the possibility of morecomplex interference modes which may allow increased control of thereflection spectra of the available states. This may include both theability to generate reflection spectra with high reflectivity over anarrow range of wavelengths, producing more vivid colours and thereby alarger colour gamut, and the ability to more independently tune thedesired reflection spectra in the multiple states of the device.Materials which may be used as sub-layers within the composite spacer orcapping layer may include (but are not limited to) ZnO, TiO₂, SiO₂,Si₃N₄, TaO and ITO. Example devices with such a composite spacer orcapping layer are illustrated in FIGS. 11-15.

FIG. 11 shows an example stack in which the capping layer 16 comprises aplurality of capping layer sub-layers 161-162. At least two of thecapping layer sub-layers 161-162 have a different refractive indexrelative to each other. Typically, at least those capping layersub-layers which are directly adjacent to each other will have differentrefractive indices relative to each other. In the particular exampleshown, the capping layer 16 comprises two capping layer sub-layers 161of a first refractive index sandwiching a single capping layer sub-layer162 of a second refractive index, different from the first refractiveindex, but other configurations are possible. In the example shown aspacer layer 40 is additionally provided between the reflective layer 12and the layer of light absorber material 10. In this particular example,the spacer layer 40 comprises a plurality of spacer layer sub-layers401-402. At least two of the spacer layer sub-layers 401-402 have adifferent refractive index relative to each other. Typically, at leastthose spacer layer sub-layers which are directly adjacent to each otherwill have different refractive indices relative to each other. In theparticular example of FIG. 11 only two spacer layer sub-layers areprovided but other embodiments may comprise more than two spacer layersub-layers. In this embodiment the stack is formed starting from asubstrate 50 beneath the reflective layer 12. As discussed below withreference to FIG. 15, this is not essential. The stack could also beformed in the reverse order starting from an optically thick cover layer70 above the capping layer 16 (in which case a substrate 50 beneath thereflective layer is optional).

In still further embodiments, examples of which are depicted in FIGS.12-14, the device further comprises a layer of passive light absorbermaterial 60. The layer of passive light absorber material 60 maycomprise a thin layer, or thin film, of light absorbing material. Thelayer of passive light absorber material 60 may be provided as part ofthe capping layer 16 (e.g. sandwiched between two capping layersub-layers), directly adjacent to the capping layer 16 (whether or notthe capping layer comprises a plurality of capping layer sub-layers), aspart of the spacer layer 40 (e.g. sandwiched between two spacer layersub-layers), and/or directly adjacent to the spacer layer 40 (whether ornot the spacer layer comprises a plurality of spacer layer sub-layers).

Without wishing to be bound by theory, the inventors currently believethat the addition of such a layer of passive light absorber materialboth contributes to increased internal reflections at the interfaces ofthis layer, and preferentially absorbs light of wavelengths havingstanding wave antinodes on the cavity or multiple cavities provided bythe other layers in the device at the location of the layer of passivelight absorber material. This again may increase the colour selectivityof the reflection spectra of the multiple states of the device,expanding the range of achievable reflected colours and/or theindependence of the colours reflected in each of the states. In anembodiment, the layer of passive light absorber material 60 is passivein the sense that it is not switchable between different states, forexample in the same way as a PCM layer. The layer of passive lightabsorber material 60 does not contain any phase-change material. In anembodiment, the layer of passive light absorber material 60 is metallic,for example formed from a metallic material such as Ag, Au, Al or Pt.The layer of passive absorber material 60 is typically designed to bethick enough to cause the desired optical effect while not being sothick as to absorb or reflect large proportions of the incident light. 3nm-30 nm has been identifies as an optimum range. To prevent oxidationof the layer of passive light absorber material 60 (e.g. in the casewhere the layer is formed from a metallic material prone to oxidation),a layer of a stable material may be deposited on one or both sides ofthe metallic layer. This layer may be thick enough (typically less than10 nm) so as not to affect the reflection spectra produced by thedevice, or may be a thicker layer which itself contributes to theintended reflection spectra. Alternatively, the layer of passiveabsorber material 60 comprises a non-metallic absorber.

FIG. 12 shows an example stack having a layer of passive light absorbermaterial 60. In this particular embodiment, the stack comprises aplurality of capping layer sub-layers 161-162. The layer of passivelight absorber material 60 is provided within the capping layer,sandwiched between two of the capping layer sub-layers 161-162.

FIG. 13 shows a further example stack having a layer of passive lightabsorber material 60. In this particular embodiment, the stack comprisesa plurality of spacer layer sub-layers 401-402. The layer of passivelight absorber material 60 is provided within the spacer layer,sandwiched between two of the spacer layer sub-layers 401-402.

FIG. 14 shows an example stack having two layers of passive lightabsorber material 60. A first of the layers of passive light absorbermaterial 60 is provided within the capping layer, sandwiched between twocapping layer sub-layers 161-162. A second of the layers of passivelight absorber material 60 is provided within a spacer layer, sandwichedbetween two spacer layer sub-layers 401-402.

Another embodiment of the invention is illustrated in FIG. 4. In thisembodiment, a layer of liquid crystal material is provided between thelight absorber layer 10 and the reflective layer 12. A transparentelectrode 21, 22 (made of e.g. ITO, 10 nm thick) is provided on eachside of the liquid crystal cavity, as is known from the art of LCDs(liquid crystal displays). The device has a transparent top layer 24,for example made of ITO, silica, alumina, zinc sulfide, or polymericmaterial, and a polarizer 26. Applying an appropriate voltage to theelectrodes 21, 22 will switch the orientation of the liquid crystalmolecules to change the refractive index of the cavity, and therebymodulate the color of the device (which can be in the form of a thinfilm, and can be pixelated).

Conventional liquid crystal devices require a certain minimum thicknessof 1 to 2 microns in order to work. This thickness is dictated by theequation:d=λ/(4Δn)where d is the minimum thickness, λ the wavelength, and Δn thebirefringence of the specific liquid crystal used in the device.

However, for the present embodiment of the invention, this equation isnot applicable because the light is modulated by changing the refractiveindex of the nano-cavity (layer 20), and not by working on the phase ofthe light as in traditional LCD devices. The result is that the liquidcrystal layer 20 can be about ten times thinner than conventionally,such as of the order of 200 nm. This means that the device can be madeultra-thin, and can switch at much higher speeds than conventionaldevices. Consequently, the device is advantageous for telecommunicationapplications. However, it can also be used for decorative applicationsthat employ color modulation with low power consumption, or for passive,reflective-type displays. Reducing the thickness of the reflective layer12 will enable color modulation in transmissive mode, and could be usedas a color filter or tuneable broadband absorber for a spectrometer.

FIG. 5 illustrates a variant on this embodiment in which the absorberlayer 10 is adjacent to the reflective layer 12 to provide a ‘leak-type’device similar to that of FIG. 1. The top layer 24 is not required.

In the devices according to the embodiments of FIGS. 4 and 5, theabsorber layer 10, such as GST, is not required to be switchable nor toshow a phase change, so does not need to be provided with its ownelectrodes. However, it can be preset in a desired phase.

FIG. 6 shows the spectral response (in reflection) for a range ofdevices according to FIG. 4 comprising, in order, an ITO top layer 24, aGST absorber layer 10, an ITO electrode 21, a liquid crystal layer 20 ofTL216, an ITO electrode 22, and a reflective layer 12 of Ag. Thethicknesses of the GST and TL216 are as given in the legend of FIG. 6.For each pair of thicknesses, plots are shown for the liquid crystalTL216 with either the ordinary (n_(o)) or extraordinary (n_(e))refractive index, obtainable by switching the liquid crystal in anelectric field applied by the electrodes 21, 22. As can be seen,significant spectral changes, and hence color changes, are apparent.

Further embodiments of the invention are illustrated in FIGS. 7 and 8.These structures are analogous to the devices of FIGS. 4 and 5 exceptthat the liquid crystal layer is replaced by an electro-optically activematerial layer 30, referred to as the EO layer 30. A transparentelectrode 31, 32 (made of e.g. ITO, 10 nm thick) is provided on eachside of the EO layer. The device of FIG. 7 has a transparent top layer34, for example made of ITO, silica, alumina, zinc sulfide, or polymericmaterial.

Electro-optically active materials change their refractive index basedon the strength of an applied electric field. Examples of EO materialsinclude: ammonium dihydrogen phosphate (ADP), potassium dihydrogenphosphate (KDP), lithium niobate, lithium tantalite, cadmium telluride,and various polymeric chromophores such as DANS, DR, FTC, CLD1, AJL8.Applying an appropriate voltage to the electrodes 31, 32 will switch therefractive index of the EO layer 30, and thereby modulate the color ofthe device (which can be in the form of a thin film, and can bepixelated).

The devices can employ very thin EO layers, such as in the range of 10to 200 nm. This means that a high electric field to cause visibleswitching can be generated even with a relatively low voltage, such as100 V or lower. Surface mount device DC-DC converters that operate up to100 V are readily available. The EO materials are all highly insulating,so practically no current is circulating, even at high voltage.Therefore energy consumption is very low, even operating at highvoltage, so battery operation is possible.

Switching speeds can also be incredibly high, such as 120 GHz, andlifetimes of huge numbers of switching cycles are achievable.Consequently, the device is advantageous for telecommunicationapplications. However, it can also be used for decorative applicationsthat employ color modulation with low power consumption, or fordisplays. Reducing the thickness of the reflective layer 12 will enablecolor modulation in transmissive mode, and could be used as a colorfilter or tuneable broadband absorber for a spectrometer.

In the devices according to the embodiments of FIGS. 7 and 8, theabsorber layer 10, such as GST, is not required to be switchable nor toshow a phase change, so does not need to be provided with its ownelectrodes.

FIG. 9 shows the spectral response (in reflection) for a deviceaccording to FIG. 7 comprising, in order, a 40 nm thick SiO₂ top layer34, a 5 nm thick GST (amorphous) absorber layer 10, a 10 nm thick ITOelectrode 31, a 20 nm LiNbO₃ EO layer 30, a 10 nm ITO electrode 32, anda 100 nm thick reflective layer 12 of Ag. The relatively flat spectrashow a black to bright transition as the voltage is decreased from +100V to −100 V. FIG. 10 shows spectral response for an example with thesame structure as for FIG. 9, except the GST is 6 nm thick, and the EOlayer 30 is CLD1 polymer in two examples with respective thicknesses of20 nm and 120 nm. As can be seen, significant spectral changes, andhence color changes, are apparent with the switch from +100 V to −100 V.

In the preceding embodiments, the liquid crystal material and the EOmaterial are both encompassed by the generic term of ‘optically activematerial’.

Materials

In many applications, the light absorber material layer 10 does notspecifically have to be a phase change material, although it can be.Examples of suitable materials for the absorber layer 10 include: any ofthe phase change materials mentioned below; plus amorphous silicon,amorphous carbon, Ge, GaAs, InAs, InP, CdTe, Ag₂S, organicsemiconductors; any suitable material that absorbs light and can bedeposited into films a few nm thick (semiconductor materials aretypically ideal for this). The stoichiometry can be changed and dopingcan be used to create the desired absorber properties. In fact, it isnot necessary to use materials that absorb light in the bulk state; suchmaterials can be engineered to create metamaterials that have thedesired properties in terms of absorption.

Many suitable phase-change materials are available, either separately orin combination, including compounds or alloys of the combinations ofelements selected from the following list: GeSbTe, GeTe, GeSb, GaSb,AgInSbTe, InSb, InSbTe, InSe, SbTe, TeGeSbS, AgSbSe, SbSe, GeSbMnSn,AgSbTe, AuSbTe, and AlSb. It is also understood that variousstoichiometric forms of these materials are possible; for exampleGe_(x)Sb_(y)Te_(z); and another suitable material is Ag₃In₄Sb₇₆Te₁₇(also known as AIST). Other suitable materials include any of theso-called “Mott memristors” (materials that undergo a metal-to-insulatortransition, MIT, at some specific temperature), for example VO_(x) orNbO_(x). Furthermore, the material can comprise one or more dopants,such as C or N.

Such so-called phase-change material (PCM), undergoes a drastic changein both the real and imaginary refractive index when switched betweenamorphous and crystalline phases. The switching can be achieved forexample by heating induced by suitable electric pulses or by a lightpulse from a laser light source, or can be thermal heating for exampleusing electrical resistive heating of an adjacent layer that is inthermal contact with the phase change material. There is a substantialchange in the refractive index when the material is switched betweenamorphous and crystalline phases. The material is stable in eitherstate. Switching can be performed an effectively limitless number oftimes. However, it is not essential that the switching is reversible.

A further enhancement applicable to all embodiments is that the materialof the layer 10 does not have to be switched simply between a fullycrystalline and a fully amorphous state. A mixture of phases can beachieved, such as 20% crystalline, 40% crystalline etc. The resultingeffective refractive index of the material is somewhere between the twoextremes of fully crystalline and fully amorphous depending on thedegree of partial crystallisation. Between 4 and 8 distinct mixed phasescan be readily achieved, having the corresponding number of differentdetectable reflectivities, but with appropriate control, the number canbe much higher, such as 128.

Although some embodiments described herein mention that the materiallayer is switchable between two states such as crystalline and amorphousphases, the transformation could be between any two solid phases,including, but not limited to: crystalline to another crystalline orquasi-crystalline phase or vice-versa; amorphous to crystalline orquasi-crystalline/semi-ordered or vice versa, and all forms in between.Embodiments are also not limited to just two states.

In the preferred embodiment, the absorber material layer 10 is composedof is Ge₂Sb₂Te₅ (GST) less than 200 nm thick.

The reflective layer 12 is typically a thin metal film, composed forexample of Au, Ag, Al, or Pt. If this layer is to be partiallyreflective then a thickness in the range of from 5 to 15 nm might beselected, otherwise the layer is made thicker, such as 100 nm, to besubstantially totally reflective.

The whole structure shown in FIGS. 1, 4, 5, 7, 8, 11, 12, 13, 14 can beprovided on a substrate 50 (shown for example in FIGS. 11-14) such as aglass, quartz, or plastics material, polycarbonate, PET etc., for easeof fabrication or structural robustness. The substrate 50 may be eitheroptically thick, so as not to affect the reflection spectra, or beprovided behind a fully opaque reflection layer 12. The layers aredeposited using sputtering in the case of inorganic material layers suchas the absorber material 10, ITO, SiO₂, and so on, which can beperformed at a relatively low temperature of 100 C or even 70 C orlower. Polymeric layers can be formed by spin-coating and curing.Additional layers may also be provided as necessary. The low temperatureprocess means that the optical device does not have to be fabricated atthe same time as the article comprising the substrate (the article mightbe, for example, window glazing); the optical device can be retro-fittedas a surface coating applied later e.g. to existing windows or panels.Alternatively, the optically important layers may be deposited inreverse order onto a transparent, optically thick, superstrate (alsoreferred to as optically thick cover layer 70), then optionallylaminated or otherwise attached to an optional substrate 50 for furtherrobustness or encapsulation. An example of such a configuration is shownin FIG. 15. In this particular example the stack comprises a cappinglayer 16, a layer of light absorber material 10, a spacer layer 40 and areflective layer 12, but it will be understood that any of the stackconfigurations disclosed herein (including stacks having multiplecapping layer sub-layers and/or multiple spacer layer sub-layers and/orone or more layers of passive light absorber material) may be formed onan optically thick cover layer 70 (with or without the additionalsubstrate 50) in a corresponding manner. The substrate 50 and/orsuperstrate 70 may be rigid such as glass or silicon, or may be flexiblesuch as polymer sheet or think flexible glass. The superstrate mayoptionally be coated with an antireflection film on the upper(viewer-side) surface for improved visibility of the coloured reflectiongenerated by the device.

Applications

Optical devices according to any of the embodiments herein can be usedas transmissive color (spectral) filters (either switchable or fixed),such as ultra-thin color filters for LCD/OLED displays and projectors.They can also be used in see-through displays, such as head-up displays(HUDs).

Optical devices according to any of the embodiments herein could be usedas transmissive security marks, applied to articles, packaging, IDbadges/passes, bank notes and so forth. A pattern can be stored in thephase change material layer by setting the crystallographic state ofdifferent regions. The pattern could simply be a recognisable image, orcould encode specific information, such as being in the form of a barcode, QR code, or other suitable code. One of the advantages of the PCMbased optical modulator is the potential for very high resolutionpatterns to be written into the device (c.f Nature 511, 206-211 (10 Jul.2014)). This allows the possibility of holographic patterns to be used.Holographic patterns may be used to diffract incident light so as toform, with or without the assistance of additional lenses or otheroptical elements, a real image, multiple real images, or a threedimensional volumetric image, at some distance or set of distances fromthe device. Holographic patterns may also be used with the device toimpart a beam steering, focusing, multiplexing or other optical effectson the input beam.

In further embodiments of the invention, as depicted schematically inFIG. 16, the stack is configured to provide a plurality of differentspectral responses to incident light in a corresponding plurality ofdifferent regions 80. In an embodiment, the different spectral responsesare provided at least partly by configuring at least a subset of theregions 80 to have different sequences of layers (more or fewer layersand/or a different sequence of layer compositions and/or thicknesses)and/or different thicknesses of one or more corresponding layers (e.g.the same compositional sequence of layers but one or more of the layersin the sequence have different thicknesses in different regions).Alternatively or additionally, the different spectral responses areprovided at least partly by configuring at least a subset of the regions80 such that the layer of light absorber material is switched intodifferent states, for example different phases. Each region mayindividually comprise any of the stacks disclosed herein. The pluralityof regions 80 may form a subset of a larger plurality of regions (whichmay also be referred to as pixels). In an embodiment the device isconfigured to provide a holographic effect, for example a holographicpattern as described above, using the plurality of different spectralresponses provided in the different regions.

In order to optimise the performance of the device for holographicapplications, the configuration of the spacer, active and passivethin-film absorber, and capping layers may be adjusted so as to givehigh contrast modulation at the specific narrow band wavelengthsintended for illumination of the device to reproduce the holographiceffect. This high contrast modulation may be amplitude based (i.e. astrong change in the reflectivity at the specific wavelength bands) orit may be a large change (ideally π or 2π radians) in the phase of lighton reflection in the multiple states. Alternatively, the configurationof the optical layers may be specified so as to give sufficientmodulation over a broad enough wavelength range to enable holographiceffects over a range of wavelengths.

A pattern is not essential because one could just relying on thepredetermined color change or spectral response intrinsic to the opticaldevice that is difficult to replicate.

In one embodiment, the security mark is on a flexible substrate, such asa smart label or ID film, which can be bent to reveal a known change incolor or to reveal a pattern to security personnel. The change in colorand/or revelation of a pattern occurs because bending the devicemodifies the thickness of the layers, particularly the spacer layer, andso changes the spectral transmission response of the device.

A further variant is when the mark is defined using a pattern of mottmemristor, such as VO_(x) or NbO_(x), as the phase change material. Achange in color contrast occurs when the mark is heated above thetransition temperature, so the security mark can be revealed by heatingthe device, and the mark disappears when it cools down again.

A device reader incorporating a simple spectrometer could assess thecolor variation of the mark at different angles (with or withoutbending) and compare that with a previously stored response to validatethe authenticity of the mark with extremely high confidence.

Another device reader uses one or more low-power laser diodes to measurethe transmissivity at fixed wavelength as a function of angle, andcompares with a known response.

In the case of a pattern written into the mark, a device reader couldinclude a camera to capture one or more images of the mark underparticular illumination wavelengths or angles, and could employ contrastcomparison and or image recognition to verify the mark.

With any of the security marks described above, the mark can, of course,be erased and/or rewritten using appropriate switching means, aspreviously described (such as laser, electric or thermal). This enablesversatile security hierarchies, for example where the user's card isverified at a first checkpoint at which the device reader also writessecond information to the mark. A second checkpoint then verifies thatthe second information is present and then erases and/or writes furtherinformation. In this way, the checkpoints can only be passed insequence; and bypassing a checkpoint will cause access as subsequentcheckpoints to be denied. The capability to write and re-write thepattern imposed on the device also allows the use of the device as adisplay or spatial light modulator, either for direct view, or to forman image at a distance from the device itself as part of a projection,or holographic projection system. When used as the light modulatingelement in a display system, the device may be configured to modulate aset of different wavelength bands in order to provide full-colourcapability. This may be achieved either by providing multiple regions inthe display with different configuration of the spacer, active andpassive thin-film absorber, and capping layers for modulation of thedifferent wavelength bands (i.e. sub-pixels within the display ofdifferent types), or the fast (typically sub-microsecond) switchingcapability of phase change material based devices may be used to providemodulation of a sequence of input colours time sequentially.

Although the spectra of FIGS. 2, 6, 9, 10 relate principally to thevisible part of the electromagnetic spectrum, transmissive-type filmscan also be used to modulate other parts of the spectrum, such asinfrared (IR) light. Thus, IR filters for transmission or reduction ofparticular bands can be fabricated. If a switchable absorber materiallayer 10 is used, then the device can be applied as a surface coatingfor glazing for thermal management e.g. for buildings. A large change intransmittance in the infrared part of the spectrum can be achievedbetween the amorphous and crystalline states of the absorber layer suchthat the change in total infrared energy transmitted through the devicecan be switched by more than 25%. Thus solar infrared light energy canbe transmitted through the glazing to provide heating for the interiorof the building, or the device can be switched to reflect more infraredto reduce unwanted heating of the interior of the building.

By appropriate choice of materials and layer thicknesses, the device canprovide a large change across the infrared part of the spectrum, whilstonly affecting the visible light to a much smaller degree. For examplethe total energy transmitted at the visible wave lengths may be effectedby less than 20%. In this way, the brightness of visible light admittedinto the building through the glazing can be maintained, while stillunobtrusively regulating the heat energy (infrared) transmitted. Inother words, the visible appearance does not necessarily change orappear tinted even when changing the infrared transmission.

Spectrometer

There is a type of spectrometer known as a broadband-filter-basedspectrometer. Light representing the spectrum to be analysed is passedthrough a broadband filter with known transmission characteristics as afunction of wavelength. Different bands are attenuated by differentamounts and the resulting light reaches a single detector which providesa single resulting total intensity value. This process is repeated withmultiple broadband filters, each of which modifies the spectrum in adifferent way. From the known transmission spectra of all of thebroadband filters, and the intensity measurements, the original spectrumcan be reconstructed computationally.

The spectrometer can be made more efficient by measuring the set ofintensities simultaneously. One embodiment for doing this employs asubstrate provided with a two dimensional array of detectors, such ascharge-coupled devices (CCDs). In front of the detector array is a setof spectral filters each comprising a transmissive filter, such aspreviously described, with a partially-reflective layer. By adjustingthe composition and/or thicknesses of the layers, the spectraltransmission of each filter can be different.

There does not have to be one filter per detector, and instead onefilter could serve multiple detector elements. Furthermore, the filtersdo not each have to be discretely fabricated.

This structure and technique makes the device simple to fabricatecheaply and quickly on a CCD array to provide a spectrometer-on-a-chip.The device can be used as a spectrometer for infrared and ultraviolet,as well as visible, and is stable on exposure to electromagneticradiation across the spectrum. The number of different filters 34 anddetectors 32 in the array can be of the order of a few hundred, or evenmany more, and this number will determine the spectral resolution. Aspectral resolution of +/−1 nm can be achieved.

A further application of any of the devices described above is as adecorative layer. For example, the lenses of sunglasses can be providedcoated with the optical device. The color and pattern could bepredetermined and/or could be changed subsequently.

The invention claimed is:
 1. An optical device comprising a stack oflayers including: a capping layer; a layer of light absorber material; areflective layer; and a spacer layer between the reflective layer andthe layer of light absorber material, wherein: the refractive index ofthe capping layer is at least 1.6; the light absorber material is aphase-change material having a complex refractive index that is settableto at least two values which confer different optical properties to thedevice; one or more electrodes are provided to enable the refractiveindex of the phase change material to be altered by application of avoltage; the spacer layer comprises a plurality of spacer layersub-layers, at least two of the spacer layer sub-layers having differentrefractive indices relative to each other; and no phase-change materialhaving a complex refractive index that is settable to at least twovalues which confer different optical properties to the device ispresent between the spacer layer and the reflective layer.
 2. The deviceof claim 1, wherein the capping layer comprises at least one of TiO₂,ZnO, diamond, SiO₂, Si₃N₄, and TaO.
 3. The device of claim 1, furthercomprising a spacer layer between the capping layer and the reflectivelayer.
 4. The device of claim 1, wherein the thickness of the lightabsorber layer is at least 10 nm.
 5. The device of claim 1, wherein thecapping layer comprises a plurality of capping layer sub-layers, atleast two of the capping layer sub-layers having different refractiveindices relative to each other, at least one of the capping layersub-layers having the refractive index of at least 1.6.
 6. The device ofclaim 1, wherein the light absorber material comprises a compound oralloy of a combination of elements selected from the following list ofcombinations: GeSbTe, VO_(x), NbO_(x), GeTe, GeSb, GaSb, AgInSbTe, InSb,InSbTe, InSe, SbTe, TeGeSbS, AgSbSe, SbSe, GeSbMnSn, AgSbTe, AuSbTe, andAlSb.
 7. The device of claim 1, further comprising a layer of passivelight absorber material, wherein the layer of passive light absorbermaterial is not switchable between different states.
 8. The device ofclaim 7, wherein: the capping layer comprises a plurality of cappinglayer sub-layers, at least two of the capping layer sub-layers havingdifferent refractive indices relative to each other, at least one of thecapping layer sub-layers having the refractive index of at least 1.6,and the layer of passive light absorber material is provided within thecapping layer, sandwiched between two of the capping layer sub-layers,or the layer of passive light absorber material is provided directlyadjacent to the capping layer.
 9. The device of claim 7, wherein: thelayer of passive light absorber material is provided within the spacerlayer, sandwiched between two of the spacer layer sub-layers, or thelayer of passive light absorber material is provided directly adjacentto the spacer layer.
 10. The device of claim 7, wherein the layer ofpassive light absorber material does not contain phase-change material.11. The device of claim 7, wherein the layer of passive light absorbermaterial is metallic.
 12. The device of claim 1, wherein one or more ofthe layers comprise an optical cavity that determines the spectralresponse of the device to incident light.
 13. The device of claim 1,wherein the stack is configured to provide a plurality of differentspectral responses to incident light in a corresponding plurality ofdifferent regions, wherein: the different spectral responses areprovided at least partly by configuring at least a subset of the regionsto have different sequences of layers and/or different thicknesses ofone or more corresponding layers; or the different spectral responsesare provided at least partly by configuring at least a subset of theregions such that the layer of light absorber material is switched intodifferent phases.
 14. The device of claim 13, wherein the device isconfigured to provide a holographic effect using the plurality ofdifferent spectral responses.
 15. A display, a color display, a securitymark, a color filter, a decorative layer, a spectrometer or a windowcomprising the optical device of claim
 1. 16. The device of claim 1,wherein one or more heating elements are provided to enable therefractive index of the phase change material to be altered byapplication of heat.
 17. The device of claim 1, wherein the device isconfigured to enable the refractive index of the phase change materialto be altered by application of light.
 18. The device of claim 1,wherein the layer of light absorber material comprises a plurality ofregions, the complex refractive index of the phase-change material ineach region being settable to at least two values independently of thephase-change material in each of the other regions.
 19. An opticaldevice comprising a stack of layers including: a capping layer; a layerof light absorber material; a layer of optically active material; areflective layer; and a spacer layer between the reflective layer andthe layer of light absorber material, wherein: the light absorbermaterial is a phase-change material having a complex refractive indexthat is settable to at least two values which confer different opticalproperties to the device; one or more electrodes are provided to enablethe refractive index of the phase change material to be altered byapplication of a voltage; the spacer layer comprises a plurality ofspacer layer sub-layers, at least two of the spacer layer sub-layershaving different refractive indices relative to each other; and nophase-change material having a complex refractive index that is settableto at least two values which confer different optical properties to thedevice is present between the spacer layer and the reflective layer. 20.The device of claim 19, wherein electrodes are provided to enable therefractive index of the optically active material to be altered byapplication of a voltage.
 21. The device of claim 19, wherein theoptically active material is a liquid crystal material and the stackfurther comprises a polarizer layer.
 22. The device of claim 19, whereinthe optically active material is an electro-optically active material.23. The device of claim 19, wherein the optically active material is aliquid crystal material less than 300 nm thick, and the stack furthercomprises a polarizer layer.
 24. The device of claim 19, wherein theoptically active material is an electro-optically active material lessthan 100 nm thick.
 25. An optical device comprising a stack of thefollowing layers: a capping layer; a layer of light absorber material; areflective layer; and a spacer layer between the reflective layer andthe layer of light absorber material, wherein: the refractive index ofthe capping layer is at least 1.6; the light absorber material is aphase-change material having a complex refractive index that is settableto at least two values which confer different optical properties to thedevice; the spacer layer comprises a plurality of spacer layersub-layers, at least two of the spacer layer sub-layers having differentrefractive indices relative to each other; no phase-change materialhaving a complex refractive index that is settable to at least twovalues which confer different optical properties to the device ispresent between the spacer layer and the reflective layer; and the stackis configured to provide a plurality of different spectral responses toincident light in a corresponding plurality of different regions,wherein: the different spectral responses are provided at least partlyby configuring at least a subset of the regions to have differentsequences of layers and/or different thicknesses of one or morecorresponding layers; or the different spectral responses are providedat least partly by configuring at least a subset of the regions suchthat the layer of light absorber material is switched into differentphases.
 26. An optical device comprising a stack of the followinglayers: a capping layer; a layer of light absorber material; a layer ofoptically active material; a reflective layer; and a spacer layerbetween the reflective layer and the layer of light absorber material,wherein: the light absorber material is a phase-change material having acomplex refractive index that is settable to at least two values whichconfer different optical properties to the device; the spacer layercomprises a plurality of spacer layer sub-layers, at least two of thespacer layer sub-layers having different refractive indices relative toeach other; and no phase-change material having a complex refractiveindex that is settable to at least two values which confer differentoptical properties to the device is present between the spacer layer andthe reflective layer, and the stack is configured to provide a pluralityof different spectral responses to incident light in a correspondingplurality of different regions, wherein either: the different spectralresponses are provided at least partly by configuring at least a subsetof the regions to have different sequences of layers and/or differentthicknesses of one or more corresponding layers; or the differentspectral responses are provided at least partly by configuring at leasta subset of the regions such that the layer of light absorber materialis switched into different phases.